Organic Free Radicals : Proceedings of the Fifth International Symposium, Zürich, 18.–23. September 1988

Front Matter....Pages I-XVI Thermal Decomposition of Indolinonic Nitroxides. A Kinetic ESR Study....Pages 1-2 Radical Cations From Alkyl Iodides and 1,n-Halogen(Alkylthio)Alkanes in Solution....Pages 3-4 Studies of β-Sulfonyl Substituted Vinyl Nitroxides....Pages 5-6 Direct and Indirect Diels-Alder Additions to Electron Rich Dienophiles....Pages 7-8 Photo-Friedel-Crafts Reaction in Synthesis of Catharanthine and its Derivatives....Pages 9-10 Hydroxyl Radical-Induced Strand Break Formation in Single-Stranded Polynucleotides and Single-Stranded DNA in Aqueous Solution as Measured by Light Scattering and by Conductivity.....Pages 11-11 Cobaloxime-Mediated Radical Cross Coupling Reactions....Pages 13-14 Magnetic Effects in the Photochemistry of Ketones....Pages 15-15 ESR Study of Reactive Intermediates in the Radiolysis and Photholysis of al Alkoxides....Pages 17-18 Rate Constants for Electron Transfer and Radical Cation Reactions of Methylated Naphthalenes....Pages 19-20 Cyclopentane Ring Formation in the Cycloaddition Reactions of 3-Butenyl Radical on the Electron-Deficinet Olefins....Pages 21-22 α-Halosulfones Reduction Mechanism: Application of Highly Efficient Radical Clocks....Pages 23-23 Tris(Trimethylsilyl)Silane. A New Reducing Agent....Pages 25-26 Autoxidation of (Me 3 Si) 3 SIH....Pages 27-27 Ti(III) Salt Mediated Radical Addition to Carbonyl Carbon, Synthesis of α,β-Dihydroxyketones.....Pages 29-29 Polarized EPR Spectra of Unstable Biradicals....Pages 31-31 Atom-Transfer Addition, Cyclization, and Annulation....Pages 33-34 Mercuric Oxide — Iodine Oxidation of Steroidal Homoallylic Alcohols....Pages 35-35 The Mechanisms of the Rearrangements of Allylic Hydroperoxides....Pages 37-38 Stereoselective C-C Bond Formation in Carbohydrates by Radical Cyclization Reactions.....Pages 39-39 A Novel Reaction of Tetracyanoethylene with N-Aryl-Isoindolines....Pages 41-42 An Electron Transfer Initiated Isomerization and Solvent Addition via Radical Cation Chain Process....Pages 43-44 Tetramethyleneethanes: Non-Kekulé Ground State Triplets at Odds with Theory....Pages 45-46 Hydrophobic Radical-Ions....Pages 47-48 Simple Synthesis of Nitroxyl Amines....Pages 49-50 Micellar Aggregation and the Decay of Triplet Radical Pairs....Pages 51-52 Spin Trapping and Matrix Isolation E.S.R. Studies of Photo-Oxidation of Alcohols by Hexachlorometallate (IV) Ions (M = PT, PD, IR)....Pages 53-54 ESR of Free Radicals in Gamma Irradiated Dna-Histone Complex....Pages 55-56 An ESR Investigation of the Photolysis of Benzene Polycarboxylate Anions in Aqueous Solution....Pages 57-58 The Effect of Temperature in the Addition of Tosyl Radicals to Arylacetylenes....Pages 59-60 Chemical Routes to Atomic Nitrogen....Pages 61-62 Hydrogen Atom Abstraction from a Molybdenum Hydride: Radical Clock Studies....Pages 63-64 Radical Cyclization of Aldehydes: Synthetic and Mechanistic Developments....Pages 65-66 Radical Addition of Acetone to Limonene Initiated by KMno 4 in Acetic Acid Medium....Pages 67-68 Three Paramagnetic Reduction Stages of Phenyl Substituted 1,2:9,10-Dibenzo[2.2]Paracyclophanes....Pages 69-70 The Role of Solvent Dynamics in Inter- and Intramolecular Electron Exchange Reactions....Pages 71-72 On the Radicalic Methylation. Unexpected Formation of Sulfones and Sulfonamides in the Reaction of Nitrosoarenes with Fenton’s Reagent in DMSO.....Pages 73-74 Theoretical Study on the Structure of β-Substituted Ethyl Radicals....Pages 75-76 Radical Reactions for Use in Organic Synthesis....Pages 77-78 Free and Unfree Radical Ions....Pages 79-79 On the Stabilization of α-Carbon Radicals by π- and Methylthio- Substituents....Pages 81-82 Seesr of Radical-Ions and of Paramagnetic Complexes....Pages 83-84 Esr Studies of 1-Silacycloalkyl and 1-Sila-Allyl Radicals....Pages 85-85 Photosensitized Generation of Singlet Oxygen ( 1 Δg) in Vivo. Proposed Biomedical Applications....Pages 87-88 Cidnp in the Reactions of Photooxidation of Benzylic Acid and Phenols Sensitized by Uranyl Ion....Pages 89-91 Stereochemical Aspects of Radical Hydroxylation of Cyclohexenes in Aqueous Solution....Pages 93-94 Regeneration of Amine in Catalytic Inhibition of Oxidation....Pages 95-96 EPR Spectra and Kinetics of some Carbonyloxyl Radicals, XCO 2 . ....Pages 97-98 The Structure of Co(II)-Corrins - ‘Nature’s Traps’ for Organic Radicals....Pages 99-100 Aspects of Organometallic Free Radical Chemistry....Pages 101-102 Endor Investigations on the Substituent Dependence of the Stabilisation of Triphenylmethyl Radicals....Pages 103-104 Hydrogen Atom Transfer Between Ketyl Radicals and Ketones....Pages 105-106 Formation of Dibenzodioxins and Dibenzofurans in Homogenous Gas-Phase Reactions of Phenols....Pages 107-108 Fragmentation Patterns for Anion Radicals in Carboxylic Acids....Pages 109-110 Unusual Transannular Radical Cyclisations....Pages 111-112 CIDNP During the Oxidation of Tertiary Aliphatic Amines....Pages 113-114 Charge Transfer Interaction Between Menadione and Nucleic Acids. A CIDNP Study.....Pages 115-116 Grignard Reaction of Ketones. Electron and Subsequent R. Transfer Processes to Ketones....Pages 117-118 Radical Ions and Photochemical Charge Transfer Phenomena in Organic Chemistry....Pages 119-120 Cyclisation of γ-Arylalkanols Via Aryl Radical-Cation and Alkoxyl Radical Intermediates....Pages 121-122 The Question of Additivity of Substituent Effects on Radical Stabilisation....Pages 123-124 Spin Delocalisation in Heterocyclic Captodative Radicals....Pages 125-126 β-Fragmentation of Alkyl Radicals. Polar and Steric Effects....Pages 127-128 The Decay Kinetics of Triplet-Triplet Fluorescence Systems. The M-Xylylene Biradicals....Pages 129-130 ESR Spectroscopy of Short-Lived Radical Pairs in Solutions....Pages 131-132 Stereochemical Effect on Intramolecular Substitutions in Induced Decomposition of Allylic Percarbonates....Pages 133-134 Gas Phase Oxygenation of Benzene Derivatives with O( 3 P) Atoms Produced by MD of N 2 O....Pages 135-136 Annulations by Reaction of Imidoyl Radicals with Unsaturated Bonds....Pages 137-138 Self Electron Transfer Reactions of Hydrazines....Pages 139-140 A Carbon-Centred Alkylphosphonate Radical Generated by Pyruvate Formate-Lyase with its Substrate Analogue Hypophosphite....Pages 141-142 Radical Ions of Benzo[ c ]cinnolines and 2,3-Dihydro-1 H -benzo[ c ]pyrazolo[1,2- a ]cinnolines....Pages 143-143 An Electron Spin Resonance Study of some Silanone Radical Anions....Pages 145-146 Nuclear-Electron Resonance in 31 P-Containing Free Radical Solution....Pages 147-148 Nitro Compounds as Free Radical Precursors....Pages 149-150 Free Radicals in the Catalytic Chemistry of Hemoproteins....Pages 151-151 Spin Trapping with Thiones....Pages 153-154 Intramolecular Motion in Organic free Radicals Studied by Muon Spin Rotation and Level-Crossing Spectroscopy....Pages 155-156 Stereochemical and Regiochemical Aspects of Free Radical Macrocyclization....Pages 157-158 Stereochemical Control in Hex-5-Enyl Radical Cyclizations....Pages 159-160 An E.S.R. Study of Aminium Radical Cations with Silyl Substitutents....Pages 161-162 The Cation-Radical of a Hindered Quinone Diazide....Pages 163-164 Free Radical Formation by Ultrasound in Aqueous Solutions of Volatile and Non-Volatile Solutes. A Spin-Trapping Study....Pages 165-166 Polarity Reversal Catalysis of Hydrogen Atom Abstraction Reactions in Solution....Pages 167-168 Kinetics and Mechanism of the Oxidation Reaction of Thioethers by Cerium(IV) Ammonium Nitrate....Pages 169-170 Nucleophilic Substitution in α-Functionalized Tertiary Haloalkanes by Resonance Stabilized Carbanions....Pages 171-172 Photoexcited Electron Transfer and Solvent-Dependent Path Ways of Spin Polarization and Radical Formation in Solutions with Anthraquinone....Pages 173-174 Photochemically Generated Radicals in Industrial Applications....Pages 175-176 Low-Field CIDNP Manifestation of the Minor Recombination Channel Via Triplet State of Radical Pairs....Pages 177-178 Chlorine-Dioxide as an Electron Transfer Oxidant of Olefins....Pages 179-179 Redox-Active Iron-Chelators based on Pyridoxal....Pages 181-182 Two Photon Processes in Free Radical Chemistry....Pages 183-184 Tetrahydrofurans, Pyrrolidines and Cyclopentanes by Intramolecular Cyclization of Kolbe-Radicals....Pages 185-186 Vitamin B 12 , Catalyst of Radical Reactions in Organic Synthesis....Pages 187-188 Solution Chemistry of Keto and Enol Cation Radicals....Pages 189-189 Hydroxyl Radical and Laser Light-Induced Strand Break Formation of Polynucleotides and DNA....Pages 191-192 Role of Nitrate Radical in the Nitrooxylation of Alkenes by Cerium(IV) Ammonium Nitrate....Pages 193-194 Ring Inversion in Dioxene Radical Cations....Pages 195-195 Antioxidant Systems in Biological Material....Pages 197-198 Cyclizing Bifunctionnalization of Dienes by Sulfonyl Halides....Pages 199-200 Radical Structure in — Irradiated Single Crystal of 17α- Hydroxyprogesterone....Pages 201-202 Enantioselective Electron Transfer During the Free Radical Chain Reduction of Ketones....Pages 203-204 Homosolvolysis....Pages 205-205 Hydrogen Transfer Activation in Radical Telomerization....Pages 207-207 Selenium Radical Cations Promoted Functional Group Transformations....Pages 209-210 Alternating Reactivity of Radicals Coordinated to Chelated Transition Metals or Metalloenzymes and Chemical Carcinogenesis....Pages 211-212 Oxidation of Crowded Polyarylphosphines and Diphosphines. ESR and Electrochemical Studies....Pages 213-214 ESR Technique in a 2mm Range of Wavelengths and its Physico-Chemical Applications....Pages 215-215 Cytochrome P450 Catalyzed Cage Radical Reactions....Pages 217-218 Single-Electron-Transfer (SET) Leading to Radical Species in the Redox Reactions of Cyclic Peroxides with Biological Substrates....Pages 219-220 Chain Transfer Mechanism in the Radical Telomerization Involving the Bromine Containing Polyhalomethanes....Pages 221-221 Free Radical Production from the Triplet State of Nalidixic Acid....Pages 223-224 New Procedures of Homolytic Alkylation of Heteroaromatic Bases: Synthesis of C-Nucleosides....Pages 225-226 Polymer-Bound Pyrylium Salts....Pages 227-228 Stabilisation and Stereodynamics of Free Radicals....Pages 229-230 Electrochemistry of Free Radicals: Substituent Effects on the Redox Potentials of Benzyl Radicals....Pages 231-232 Dissociation and Ion-Molecule Reactions of Alkane Radical Cations. Time-Resolved FDMR....Pages 233-233 Endor of Metalloproteins at X-Band and Q-Band Microwave Frequencies....Pages 235-235 Why Bromine is Used in the Autoxidation of P-Xylene to Terephthalic Acid....Pages 237-238 Back Matter....Pages 239-251